Composition of matter and method of making same



.Patentecl Sept. 12, 1944 COMPOSITION OF MATTER AND METHOD OF SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Application August 2, 1943,

Serial No. 497,125

8 Claims.

This invention relates to a new chemical prodnot or composition of matter, our present application being a continuation-in-part of our pending application Serial No. 447,158, dated June 15, 1942.

The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifler in the resolution of crude oil emulsions.

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound.

Although one of the primary objects of our invention is to provide a new compound or composition of matter that is an eiiicient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is adapted for use in other arts, as hereinafter indicated. It also may have additional uses in various other fields which have not yet been investigated.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over 8 carbon atoms,

and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of v new compositions of matter which have utility in various arts, and particularly in the demulsification of crude oil.

The compounds herein contemplated may be produced in any suitable manner, but are usually manufactured by following one of two general procedures. -In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described,

and momentarily indicated by the formula R1(OH)1n. Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The'second procedure is to react an alcoin which n" has the value of one, or two.

Glycerol may be conveniently indicated by the following formula:

\ 0H caut on If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the-following formula:

(CIH4O).IH

CaHt0a-(C:H4O),.'H

(CIHAO).'H

in which the value of 1: may vary from 3 to 10 and all the values of n need not be identical. If a polybasic carboxy acid be indicated by the formula:

coon

RCOOH coon then the acyclic reaction product of one mole ilarly, if two moles of the polybasic acid be used. then the compound may be indicated by the following formula:

(cgnlowoocmcoonm canioHcinlmtoocR coon cinlown Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

cinlowoocmcoomn cantorwinlowoocswoon cinlowoocmcoonm If a fractional ester of the kind exemplified by the three preceding formulas is reacted with one or more moles of an alcohol 01 the kind previously described in a generic sense as R1(0H)m, then obviously, one may. obtain a material of the type indicated by thefollowin formula: v

[(C1H|0)-.,I0OCR(COOH)-"]' inwhichrcisO,1or2,yis0,1or2,andzis 1,2 or 3, and x is or 1, and 1/ is 1 or 2.

It has been previously stated that compounds of the type herein contemplated may be ob- .tained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking by the unitary structure CnHimO, is included within the meaning of the hereto appended claims and may be simply considered as a variant of propylene oxide, i. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an 'alicyclic alcohol. It may also be converted into an amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broader scope, as follows:

in which n replaces the numbers 2, 3 or 4,'Z includes the acidic hydrogen atom itself. In the above formula and hereafter, for convenience, R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most likely to result.

The production of the compounds herein contemplated is the result of one or more esterification steps. As is well known, esterification procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one of several procedures. One procedure is to pass an inert dried gas through the mass to be esteriiied, and have present at the same time a small amount of a catalyst, such as dried 1101 gas, a dried sulfonic acid, or the.

like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts, and for convenience, reference is made to U. S. Patent No. 2,264,759,1dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulas-indicating the compounds under consideration, it can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that underv suitable conditions, instead of obtaining the monomeric compounds indicated, one'would in reality obtain a polymer in the sense, for example, that polyethylene glycols represent a polymer of ethylene glycol. The term polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the monomer. In the present instance, however.. polymerization involves the splitting and loss of water so that the process is essentially self-1 esterlfication. Thus, strictly speaking, the polymeric compounds are not absolutely polymers of the monomeric compounds, but since, for'all practical purposes, they can be so indicated,

self-esteriilcation products of the monomeric compounds.

In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are balsaun-like and sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitarystructure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not, herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polysoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.)

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain. neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl, or at least, one free hydroxyl, orboth. The word polar" has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or, at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal, an ammonium radical, a substituted ammonium radical, etc. In the hereto appended claims the word polar" is used in this specific sense.

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they :may be derived from acyclic diglycerol, triglycerol, tetraglycerol, mixed polyglyc-. erols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether, and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyalkylation and then employed. in the same manner as oxyaikylated glycerol, is employed in the present instance, are not contemplated in this specific case, although attention is directed to'the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a co pending application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom, particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyDacetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our application Serial No. 384,600, filed March 21, 1941, now U. S. Patent No. 2,295,168, dated September 8, 1942. Said patent involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, where'- as, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms, or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product, 'although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obbenindustrie, A. G.)

tamed by oxyethylation, although-as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately 15 to 24 oxyethylene groups havebeen introduced into a single glycerol molecule. This means that approximately flve to eight oxyethylene radicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11 of German Patent No. 605,973, dated November 22, 1934, to I. G. Far- The procedure indicated in the following three examples issubstantially identical with that outlined in said aforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 184 pounds of glycerol is mixed with /2%, by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from -180 C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol.

OxYa'rnYLArEn GLYCEROL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXYETHYLATED GLYCEROL Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to 1.

OXYETHYLATED GLYCEROL MALEATE Example 1 OXYETHYLATED GLYCEROL MALEATE Example 2' The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

referred to as hydroxylated wax acids.

oxnrmliun GLYCIROL Mun" Example 3 The same procedure is followed as in the two preceding examples, except that three moles oi maleic anhydride are employed so as to obtain the trimaleate.

OXYETHYLATED Gnxcsnor. MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio I to 18) is substituted inplace oi oxyethylated glycerol (ratio 1 to 15).

Oxxarnxtnsn GLYCEROL MALEATE Example 5 The same procedure is employed as in the preceding examples. except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylatedglycerol (ratio 1 to or (1 to 18).

Previous reference has been made to an alcoholic body which has been defined generically hydroxy acids and also by the fact that there is no residual hydroxyl radical attached to the polybydric alcohol residue; i. e., the compounds are neutral or complete esters, as differentiated from fractional esters. The polyhydric alcohols employed as reactants for the production of the neutral esters of the high molal hydroxy acids are characterized by the fact that they contain three hydroxyl groups, the commonest example being glycerol. Trihydric'alcohols may be obtained by etherization reactions involving monohydric alcohols and polyhydric alcohols having more than three hydroxyl radicals, as, for example, diglycerol, pentaerythritol, mannitan, sorbitan, etc. The ethyl ether, butyl ether, or other alkoxy derivatives of diglycerol, is an additional illustration of this particular type. Any trihydric alcohol, i.'e., any triol, can of course be treated with an alpha-beta alkylene oxide, such as ethylene oxide, propylene oxide, or the like, so as to add an alkoxy group and still retain a terminal hydroxyl group. The oxyalkylation of glycerol by means of ethylene oxide illustrates this type. It is not intended to include ether alcohols, particularly ether glycerols, in which the ether linkage occurs more than four times.

The trihydric alcohols or triols just described are esterified with or converted by any suitable means, into water-insoluble esters of high molal hydroxy acids having at least 8 carbon atoms and not in excess of 36 carbon atoms. The commonest example of a high molal hydroxy acid isricinoleic acid.

"Other hydroxy fatty acids include hydroxystearic acid, dihydroxystearic acid, diricinoleic acid, aleuritic acid, and the like. Similar acids are obtained in the oxidation of paraffin, petro leum hydrocarbons, or wax, and are commonly droxylated wax acids occur as by-products in the oxidation of waxes or similar materials, and.

are usually separated so that the commonest commercial form of oxidized wax acids represent mixtures comparatively free from the hydroxylated compounds. Hydroxylated acids are produced by other procedures, such as chlorinaaaumao tion, either by addition or substitution, as, for

example, chlorination of oleic acid or stearic acid. Subsequent reactions involve the removal of the chlorine with the introduction of a hydroxyl radical. Undecylenic acid, derived from castor oil, has been converted into a hydroxy undecenoic acid. Unsaturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as-to produce derivatives, for example, chlorinated or brominated ricinoleic acid. Such materials are entirely satisfactory for use as reactants in the preparation of materials of the kind herein contemplated. Naturally-occurring naphthenic acids can also be converted into hydroxylated products by following similar procedure. An unsaturated hydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such as those involving ricinoleic acid, benzene, and aluminum chloride in large excess, or involves the desulfonation of a sulfoaromatic fatty acid. In any event, by employing derivatives of undecylenic acid, or one or more of the various wax acids, naturallyoccurring naphthenic acid, ricinoleic acid, diricinoleic acid, or derivatives thereof, as have been enumerated, one can obtain a variety of hydroxylated mono-carboxy acids, having at least 11 carbon atoms and not in excess of 36 carbon atoms. Such compounds are the kind herein contemplated as reactants to furnish the alcoholiform hydroxyl.

Hydroxy acids of the kind herein contemplated may also be prepared by the hydrolysis of alphahalogen acids. For instance, alpha-bromocaproic acid, alpha-bromocaprylic acid, alphabromocapric acid, alpha-bromolauric acid, alpha-bromomyristic acid, alpha-bromopalmitic acid, and the like, can be hydrolyzed to give the corresponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent of an alpha-hydroxy acid by liberation of hydrochloric acid, instead of water. Such type of reaction, however, involves numerous difliculties; and thus, it is better to employ a hydroxy acid.

In some instances, derivatives of a hydroxylated unsaturated acid are most readily obtained by the employment of an intermediate in which the hydroxyl group is protected. Thus, ricinoleic acid may be acetylated, and such acetyl ricinoleic acid converted into a derivative, for

I instance, a derivative in which an aryl group See also Organic Syntheses, volume X, page 88, r

COMPLETED MONOMERIC DERIVATIVE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol maleate, Example 1 is reacted with one pound mole of triricinolein, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difllculty. In other instances, however, such high boiling inert vaporizing solvent, if employed, might be permitted to remain in the reacted mass and appear-as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about 180 to 200 C. and time of reaction about 20 hours.

COMPLETED MONOMERIC DERIVATIVE Example 2 The same procedureis followed as in Completed monomeric derivative, Example 1, preceding. except that the dimaleate described under the heading Oxyethylated glycerol maleate, Ex-

ample 2'" is used instead of the monomaleate.

COMPLETED MoNoivIERIc DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the dimaleate, or each pound mole of the trimaleate, instead of using one pound mole of triricinolein, as a reactant, one employs two pound moles.

COMPLETED MONOMERIC DERIVATIVE Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of triricinolein, one adds three pound moles of triricinolein for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For

, example, one indicated by the ratio of 1 to 21.

(See Oxyethylated glycerol maleate, Example 5, preceding.)

COMPLETED MoNoMERIc DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that succinic anhydride is employed as a reactant instead of maleic anhydride.

COMPLETED MoNoMERrc DERIVATIVE I Example 9 The same procedure is followed as in Examples 1 to 7, preceding, except that adipic acid is employed instead of maleic anhydride.

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boiling point of water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esteriflcation step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through the mixture. Sometimes it is desirable to add an esterification catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U. S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esteriflcation is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to'carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is-separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances Where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance.

In many cases when the compound is manufactured for purposes of demulsification, one is better oil to obtain a polymer in the sense previously described, particularly a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular Weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in View of the effectiveness of the low multiple polymers as demulsifiers. .Pre- Vious reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents including organic radicals, for instancathe radicals obtained from alis absolutely apparent.

from such materials as ricinoleic acid to oleic.

acid, including alcohol acids, such as hydroxy acetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that by-products or cogeneric materials were formed, may be recapitulated with great definiteness, and one can readily appreciate that the formation of heatrearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heatrearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esteriflcation monomers, separately and jointly. Although the class of materials speciflcally contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramiiication, except in a manner employed in the hereto appended claims.

Although the products herein contemplated var so broadly in their characteristics, 1. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, sub-resinous materials, semiresinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used as the raw 'materialwhen our new product is used as a demulsifler in the resolution of oil field emulsions, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, Such statement. is an obvious oversimpliflcation of the rationale underlying demulsification, and does not even consider. the resistance of an interfacial film to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidiflcation polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED PoLYMERIc D aIvATIvEs INCLUDING HEAT-REARRAILGED COGENERS Example 1 One pound mole of oxyethylated glycerol dimaleate is reacted with one pound mole of triricinolein, with constant stirring, for a period of two. to 60 hours, at a temperature of 220-240 C., so as to eliminate suillcient water in order to insure that the resultant product has a molecular weight approximately twice that of the monomeric material.

COMPLETED POLYMERIC DEnIvATIvEs INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENERs Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that chlorinated triricinolein is substituted in place of triricinolein.

COMPLETED POLYMERIC DEaIvATIvEs INCLUDING HEAT-REARRANGED COGENERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a, single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4,

COMPLETED are mixed in molecular proportion and subjectedto polymerization in the matter indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result of a two-step procedure. In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step.

' Indeed, the formation of the monomer and poly- 220 C. until the mass is either homogeneous or shows two separate layers, each of which is homogeneous per se. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearv ranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reac tion stage there is formed, to a greater or lesser degree, suillcient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material,

which is sticky or sub-resinous in nature. In many instances, it will be found that the thinner liquid material is a-monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by

. separating the two heterogeneous phases and emrations; as a. flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and thelike; as germicides, e

cides, emulsifiers for cosmetics, spray oils, waterrepellenttextile finish, etc. These uses are by no means exhaustive.

However, th most important phase of the present invention, as far as industrial application goes, is concerned with the use of the materials previously described as demulsiflers for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are efiective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsiflers, or in particular as surface tension depressants in combination is one of a.series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 497,118, 497,119, 497,120, 497,121, 497,122, 497,123, 497,124, 497,126, 497,127, 497,128, 497,129, 497,130, 497,131, 497,132, 497,133, 497,134 and 497,135, all filed August 2,1943.

Having thus described our invention, what we cleilm as new and desire to secure by Letters Paten is:

1. An ester, being a member of the class consisting of monomers, sub-resinous esteriilcation polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

' ucnzhowooomooozln' llolmor- (c..n,..o ..'m,

in which R is the carboxyl-free radical of a polycarboxy acid having not over 8 carbon atoms;

R1 is a water-insoluble completely esterified trihydric alcohol ester radical of which the acyl radicals are 'high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the numerals 1 to 2; n: represents the numerals 0 to 2; y represents the numerals 0 to 2; 2 represents the numerals 1 to 3; 0: represents the numerals 0 to 1; and y represents the numerals l to 2.

2. An ester, being a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

in which R is a. carboxyl-free radical of a. dicarboxy acid having not over 6 carbon atoms;

R1 is a water-insoluble completely esterifled trihydric alcohol ester radical of which the acyl radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; it represents the numerals 2 to 4; n represents the numerals 3 to 10; .1: represents the numerals'O to 2; 3 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

3. An ester, being a. member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esterifled trihydric alcohol ester radical of which the acyl radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

4. An ester, being a. polar member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogeneric sub-resinous heathydric-alcohol ester radical of which the acyl rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms;

R1 is a water-insoluble completely esterifled trilo radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; 1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

5. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers. and cogeneric sub-resinous heat-rearranged derivatives thereof, and

of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble completely esteriiied trihydric alcohol ester radical of which the acyl radicals are high molal hydroxy acid radicals having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; 3: represents the numerals 0 to 2; 1 represents the numerals 0 to 2; and .2 represents the numerals l to 3.

6. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

[(cunohoocnc 0oz KCIHIOMHL ,Hi0 o 001100031 in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms: R1 is a water-insoluble completely sterified triol ester radical in which the acyl radicals contain 18 carbon atoms and at least one hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; 1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

'7. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterlfication polymers, and cogenerlc sub-resinous heat-rearranged derivatives thereof, and of the following formula:

[((hmowoocac 0oz ClHlOPKCIHiCDmH],

[(CzHrOLuOO CRCOO R in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a triricinoleic radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n' represents the numerals 3 to 10; 0: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerails 1 to 3.

8. A method for manufacturing esters as delined in claim 1, consisting of reacting an oxya'lkylated glycerol with a polycarboxy acid having not over 8 carbon atoms, and subsequently reacting said intermediate with a water-insoluble completely esterifled trihydric alcohol ester of a high molal hydroxy acid having at least 8 and not more than 32 carbon atoms.

' MELVIN DE GROOTE. BERNHARD KEISER. 

